The present invention relates to processing compositions for silver halide photographic materials and image forming methods using the same, and, in particular, to such compositions and methods that can effectively suppress stain generation caused by spectral sensitizing dyes remaining in the photographic materials after processing, and that do not form precipitates even when the processing compositions are kept under low temperature storage conditions.
In the rapid progress of digital still cameras as well as various color printers, the processing of silver halide color photographic materials are expected to provide customers with high quality images as quickly as possible. When the time of the conventional photographic processing is simply curtailed, spectral sensitizers used in photographic materials tend to remain after processing because the processing terminates before the sensitizers are completely washed out from the materials. In the case of color print, a noteciable amount of remaining sensitizers causes the background of the print images to assume color, thus deteriorating the print appearance to an unacceptable level. A similar problem takes place for the highlights of color reversal films with a simple curtailing of processing time. In color negative films, the minimum density levels tend to rise, causing color balance to collapse to such a degree that favorable prints cannot be obtained.
Research Disclosure (RD) 20733 describes a method using bis(triazinylamino)stilbene disulfonic acid compounds to effectively remove stains caused by spectral sensitizers. This method is now in a wide use for the processing of color photographic materials. JP-A-6-329936 (the term xe2x80x9cJP-Axe2x80x9d as used herein means an xe2x80x9cunexamined published Japanese patent applicationxe2x80x9d) discloses bis-triazynyldiaminostilbene disulfonic acid compounds that can suppress stains even in rapid processing.
Recently, however, a still more concentrated processing compositions are strongly demanded to reduce container waste, improve container recyclability, reduce transportation and storage costs, etc. There have been no compounds that stably dissolve at a high salt concentration and that, when used in their solubility limit, exhibit a sufficient effect at rapid processing.
The purpose of the present invention is to provide processing compositions for silver halide color photographic materials, wherein the compositions can effectively prevent stain formation caused by residual spectral sensitizers and the compositions do not form precipitate under low temperature storage conditions.
Another purpose of the present invention is to provide methods of forming photographic images which can suppress stain generation by using processing compositions that do not form precipitate under low temperature storage conditions.
The above-mentioned problems have been solved by the following present invention.
(1) A processing composition for a silver halide photographic material, which comprises at least one compound selected from the group consisting of compounds represented by the following general formulae (I) and (II): 
wherein R11 and R12 each independently represents a hydrogen atom or an alkyl group; R13 and R14 each independently represents a hydrogen atom, an alkyl group or an aryl group; R15 represents an alkyl group having at least one asymmetric carbon atom or a group represented by the following general formula (I-a):
xe2x80x94CH2O(CH2CH2O)n11Hxe2x80x83xe2x80x83(I-a) 
wherein n11 represents an integer of from 1 to 3; R16 represents an alkyl group having at least one asymmetric carbon atom or a group represented by the following general formula (I-b):
xe2x80x94(CH2CH2O)n12Hxe2x80x83xe2x80x83(I-b) 
wherein n12 represents an integer of from 2 to 4; and M1 represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or a pyridinium group, R13 may complete a ring together with R15, and R14 may complete a ring together with R16, respectively: 
wherein R21, R22, R23 and R24 each independently represents a hydrogen atom, an alkyl group or an aryl group; R25 and R26 each independently represents an alkyl group having at least one asymmetric carbon atom or a group-represented by the following general formula (II-a):
xe2x80x94(CH2CH2O)n21Hxe2x80x83xe2x80x83(II-a) 
wherein n21 represents an integer of from 2 to 4; R27 and R28 each independently represents an alkyl group having at least one asymmetric carbon; and M2 represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or a pyridinium group; and R21 and R25, R22 and R26, R23 and R27, and R24 and R28, each pair may be bonded together to form a ring.
(2) The processing composition described in (1) above, wherein the composition contains at least one of the compound represented by general formula (I) in which R15 and/or R16 contains at least one hydroxyl group and the compound represented by general formula (II) in which at least one group chosen from R25, R26, R27 and R28 contains at least one hydroxyl group.
(3) The processing composition described in (2) above, wherein the at least one of the compound represented by general formula (I) and the compound represented by general formula (II) has 2 to 8 hydroxyl groups.
(4) The processing composition described in (3) above, wherein R11, R12, R13 and R14 in general formula (I) and/or R21, R22, R23 and R24 in general formula (II) each is a hydrogen atom.
(5) The processing composition described in (1) above, wherein the compound represented by general formula (I) is selected from the group consisting of the following compounds: 
and the compound represented by general formula (II) is selected from the group consisting of the following compounds: 
(6) The processing composition described in any one of (1) to (5) above, that is a color developer composition.
(7) The processing composition described in any one of (1) to (6) above, that has a pH of from 12 to 13.5.
(8) The processing composition described in any one of (1) to (7) above, that is a one-part color developer composition.
(9) An image forming method comprising using the processing composition described in any one of (1) to (8) above.
(10) A method for reducing stain caused by residual sensitizing dyes in silver halide photographic materials, which comprises using the processing composition described in any one of (1) to (8) above.
Among the compounds of the present invention, the structure represented by general formula (I) is involved in the claims of JP-A-6-332127, JP-A-7-140625 and JP-A-10-104809. However, these specifications do not specify the specific compounds corresponding to those of the present invention at all. Therefore, it is impossible to predict the structures and properties of the compounds of the present invention from these patent documents.
General formulae (I) and (II) will be explained more in detail.
The alkyl groups represented by R11 and R12 are preferably of C1-20, more preferably of C1-8, and still more preferably of C1-4; they may be substituted or unsubstituted. The substituents include a hydroxyl group, an alkoxy group (e.g., methoxy, ethoxy, etc.), a sulfonic acid group, an ethyleneoxy group, etc. These groups may be further substituted with the groups mentioned above. Practical examples of the alkyl groups represented by R11 and R12 are methyl, ethyl, n-propyl, iso-propyl, n-octyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-sulfoethyl, 2-methoxyethyl, 2-(2-hydroxyethoxy)ethyl, and 2-[2-(2-hydroxyethoxy)ethoxy]ethyl, and 2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethyl. Preferable examples of R11 and R12 are hydrogen, methyl, ethyl, n-propyl, n-butyl and 2-sulfoethyl, and more preferable ones are hydrogen, methyl, ethyl, and 2-sulfoethyl while the most preferable ones are hydrogen and methyl.
The preferable numbers of carbon atom, the preferable substituents, the practical examples for the alkyl groups represented by R13, R14, R21, R22, R23 and R24 are all common to those for the groups represented as R11 and R12, except that R21 and R22 each never represents xe2x80x94CH2CH2SO3M1 in which M1 has the same meaning as in general formula (I). The aryl groups represented by R13, R14, R21, R22, R23 and R24 are preferably of C6-20, more preferably of C6-10, still more preferably of C6-8: they may be substituted or unsubstituted. The substituents include hydroxy, alkoxy (e.g., methoxy, ethoxy, etc.), carboxy, alkyl (e.g., methyl, ethyl, propyl, etc.), sulfonyl, amino, carbamoyl, etc. These substituents may further be substituted with the same groups cited above. Practical examples of the aryl groups represented by R13, R14, R21, R22, R23 and R24 include phenyl, naphthyl, 3, 5-dicarboxyphenyl, 4-methoxyphenyl and 3-isopropylphenyl. More preferable groups are hydrogen, methyl, ethyl, n-propyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-sulfoethyl, 2-(2-hydroxyethoxy)ethyl or 2-[2-(2-hydroxyethoxy) ethoxy]ethyl, and still more preferably they are hydrogen, methyl, ethyl, 2-hydroxyethyl, 2-hydroxypropyl or 2-(2-hydroxyethoxy)ethyl. The most preferable examples are hydrogen and methyl.
The alkyl group represented by R15 having at least one asymmetric carbon atom is preferably of C1-20, more preferably of C1-8 and particularly preferably of C1-4 with straight, branched or circular chains. The preferable substituents include hydroxy, amino, carboxyl, etc., the most preferable one being hydroxy. Some practical examples for the alkyl group represented by R15 having at least one asymmetric carbon atom are shown below. 
Among these formulae, preferable alkyl groups represented by R15 having at least one asymmetric carbon are 2), 3), 5) 8), 9) and 11), and more preferable ones are 2), 5) and 11). Further, when R15 is represented by the following general formula (I-a), n11 is preferably 1 or 2 and more preferably 1.
xe2x80x94CH2O(CH2CH2O)n11Hxe2x80x83xe2x80x83(I-a) 
The alkyl groups represented by R16, R25, R26, R27 and R28 having at least one asymmetric carbon are preferably of C1-20, more preferably of C1-9, and still more preferably of C1-5; their chain structures may be straight, branched or circular. Preferable substituents are common to those mentioned for R15; one of the preferable groups being hydroxy. Some practical examples of the alkyl groups represented by R16, R25, R26, R27 and R28 having at least one asymmetric carbon are shown below. 
Among these alkyl groups represented by R16, R25, R26, R27 and R28 having at least one asymmetric carbon, preferable ones are 17), 18), 20), 23), 24) and 26), and more preferable ones are 17), 20) and 26). When R16 is represented by the following general formula (I-b), n12 is preferably 2 or 3, and is more preferably 2.
xe2x80x94(CH2CH2O)n12Hxe2x80x83xe2x80x83(I-b) 
When R25 and R26 are those represented by the following general formula (II-a) n21 is preferably 2 or 3, and more preferably 2.
xe2x80x94(CH2CH2O)n21Hxe2x80x83xe2x80x83(II-a) 
Among the alkali and alkaline earth metal atoms represented by M1 and M2, particularly preferable ones are Na and K. Tetra-alkyl ammonium such as tetraethyl ammonium and tetrabutyl ammonium is preferred as ammonium group. The most preferable metals for M1 and M2 are Na and K.
Among the compounds represented by general formula (I) those in which at least either of R15 and R16 includes at least one hydroxyl group are preferred. In general formula (II), at least one group among R25 to R28 should preferably have at least one hydroxyl group, too.
The most preferable compounds represented by general formula (I) are those as follows; each of R11, R12, R13 and R14 is hydrogen or methyl, R15 is an alkyl represented by 2), 5) or 11) mentioned above, nil in formula (I-a) is one, R16 is an alkyl shown in 17), 20) or 26) mentioned above, n12 in formula (I-b) is 2, and M1 is Na or K. On the other hand, the most preferable compounds represented by general formula (II) are the following ones; each of R21, R22, R23 and R24 is hydrogen or methyl, R25 and R26 each is alkyl shown in 17), 20) or 26) cited above, n21 in formula (II-a) is 2, R27 and R28 each is alkyl shown in 17), 20) or 26), and M2 is Na or K.
As the compounds used in the present invention contain plural asymmetric carbon atoms in the molecular structure, a number of steric isomers exist for a structural formula. The present invention covers every possible steric isomer. Only one isomer or mixtures of existing steric ones may be used.
In the present invention, together with the compounds represented by general formulae (I) and (II), plural kinds of additional diaminostilbene compounds may be used. As such additional compounds, the diaminostilbenes represented by general formula [III] disclosed in JP-A-6-329936 are preferred.
Further, diaminostilbene compounds additionally used in the present invention include known or commercially available diaminostilbene type fluorescent whitening agents. Some commercially available compounds are described in, for example, pp. 165 to 168 of Senshoku Note (Dyeing Note), 19th Edition (Shikisensya Co., Ltd.). Among those described there, Blankophor BSU liq and Hakkol BRK (both being product names) are preferred.
In the following, representative examples of the compounds represented by general formulae (I) and (II) that are suited for the present invention are listed where Me and Et mean methyl and ethyl group, respectively. 
The compounds represented by general formula (I) or (II) can be synthesized by referring to the descriptions in the paper by Koji Matsui, published in Yuki Gosei Kagaku Kyokai-shi (The Bulletin of Organic Synthesis Association), Vol. 17, p. 528 (1959), and U.S. Pat. No. 2,618,748. Preferably, a diaminostilbene derivative is reacted first with cyanuryl chloride and then with an amine. Alternatively, it is desirable to make the dialkylaminostilbene derivative react finally. The solvent used for such reactions includes water and organic solvents such as alcohols, ketones, ethers, amides, etc. In particular, water, water-soluble organic solvents and their mixtures are preferred. The most preferable are mixed solvents of water and acetone. The base used for the synthesis include organic bases such as triethylamine, pyridine, 1,8-diazabicyclo[5,4,0]-7-undecene, etc., and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydride, etc. Among them, inorganic bases, in particular, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate are preferred. The reaction temperature can be set between xe2x88x9220 and 120xc2x0 C. A preferable range is xe2x88x9210 to 90xc2x0 C. In more detail, the preferable range is xe2x88x9210 to 10xc2x0 C. for the first step, 0 to 40xc2x0 C. for the second step, and 50 to 90xc2x0 C. for the third step, respectively.
By following the reaction sequence described by the following chemical reactions, an exemplified compound (I-1) for the present invention was synthesized. 
(Synthesis of Compound (3))
In a three neck flask, 103.5 g of compound (1) and 680 ml of acetone were charged. The system was cooled with an ice-acetone bath until the temperature of the content became xe2x88x925xc2x0 C. when a aqueous solution comprising 101.9 g of compound (2), 58.3 g of sodium carbonate and 960 ml of water was added drop-wise under stirring over the period of an hour. Then the temperature of the content was increased to xe2x88x921xc2x0 C. After the addition, the content was stirred for another hour with the ice-acetone bath removed to give rise to a crystalline deposit, which was filtered by suction to obtain the target-compound (3). The filtered product was used for the next procedure without drying and purification.
(Synthesis of Compound (4))
The compound (3) thus obtained and 1.9 liters of water were charged in a three neck flask placed in a water bath, to which 68.8 g of taurine was first added under stirring. Then, 58.3 g of sodium carbonate dissolved in 275 mL water was added drop-wise over the period of one hour. After the addition, the water bath was removed and stirring was continued for 3 hours. Then, 550 g of sodium chloride was added, and stirring was extended for another hour to form a crystalline deposit, which was filtered by suction to obtain the target compound (4). The filtered product was used for the next procedure without drying and purification.
(Synthesis of Exemplified Compound (I-1))
A three neck flask was charged with compound (4) obtained by the previous step and 825 ml of water. At room temperature, 125.3 g of compound (5) was added drop-wise in 10 min. After the addition, with keeping the inner temperature of the flask at 85xc2x0 C., stirring was continued for 3 hours, and the resulting reaction mixture was concentrated with a rotary evaporator. At the point where the residual volume became about 800 mL, crystals began to deposit. The rotary evaporation was stopped, and the content was cooled by ice and subjected to stirring. The crystalline deposit was filtered by suction, and then dissolved in 1.5 L methanol. The solution was stirred for one hour under heat refluxing. When the solution was cooled to room temperature, the target exemplified compound (I-1) separated, which was filtered by suction to give 206.0 g of the target exemplified compound (I-1) (yield: 72%).
xcexmax(H2O)=346.3 nm (xcex5=4.83xc3x97104) 
The purity of the resulting product investigated with liquid chromatography proved to be 96.0%. The detailed conditions for liquid chromatography were as follows:
Column: TSK-gel ODS-80TM (a product of Tosoh Corporation)
Eluent: Liquid A To 1 L water, 20 mL PIC A reagent (a product of Waters Co.) was added.
Liquid B To the mixture of 800 mL methanol and 200 mL water, 20 mL PIC A reagent was added.
A gradient was applied so that Liquid A/Liquid B=50/50 (0 min.) 0/100 (35 min.)
Detection wavelength: 346 nm
The purity was calculated from the peak area recorded on the chart under the above conditions.
By following the reaction sequence described by the following chemical reactions, an exemplified compound (I-20) for the present invention was synthesized. 
(Synthesis of Exemplified compound (I-20))
A three neck flask was charged with compound (4) that had been prepared in the same scale via the same procedures as those described in Synthesis Example 1 and 825 mL water. To the flask, 144.4 g of compound (6) was added dropwise in 10 min under stirring at room temperature. The content was stirred for 3 hours at 85xc2x0 C. after the addition, and then condensed with a rotary evaporator until the volume be about 800 mL. Stirring was continued under ice cooling to cause crystals to separate. The crystalline deposit filtered by suction was dissolved in 1.5 L methanol and stirred for an hour under heat reflux. The solution was cooled to room temperature, and filtered by suction to obtain 249.7 g of the target exemplified compound (1-20) (yield: 85%).
xcexmax(H2O)=354.5 nm (xcex5=4.92xc3x97104) 
The purity of the target compound proved to be 97.3% with liquid chromatography carried out under the same conditions as in Synthesis Example 1.
By following the reaction scheme below, an exemplified compound (I-33) for the present invention was synthesized. 
(Synthesis of Exemplified compound (I-33))
A three neck flask was charged with compound (4) that had been prepared in the same scale via the same procedures as those described in Synthesis Example 1 and 825 mL of water. To the flask, 268.5 g of compound (7) was added dropwise in 10 min under stirring at room temperature. The content was stirred for 3 hours at 85xc2x0 C. after the addition, and then condensed with a rotary evaporator until the volume was reduced to about 900 mL. Stirring was continued under ice cooling to cause crystals to separate. The crystalline deposit filtered by suction was dissolved in 1.5 L methanol and stirred for an hour under heat reflux. The solution was cooled to room temperature, and then filtered by suction to obtain 302.4 g of the target exemplified compound (1-33) (yield: 88%).
xcexmax(H2O)=348.6 nm (xcex5=4.36xc3x97104) 
The purity of the target compound proved to be 96.1% with liquid chromatography carried out under the same conditions as in Synthesis Example 1.
By following the reaction scheme below, an exemplified compound (II-5) for the present invention was synthesized. 
(Synthesis of Exemplified compound (II-5))
A three neck flask was charged with compound (3) that had been prepared in the same scale via the same procedures as those described in Synthesis Example 1 and 825 mL of water. To the flask, 256.0 g of compound (5) was added dropwise in 30 min under stirring and water cooling. The content was stirred at 85xc2x0 C. for 5 hours after the addition, then cooled with ice below 15xc2x0 C., and added with 500 mL conc. hydrochloric acid. Further, with the addition of 2 L acetone, ice cooling was stopped Two hours stirring gave rise to a crystalline precipitate, which was filtered with suction. The crystalline precipitate was dissolved in 1 L methanol and stirred for an hour under heat reflux. The solution was cooled to 30xc2x0 C., and then filtered by suction to obtain 216 g of the target exemplified compound (II-5) (yield: 87%).
xcexmax(H2O)=346.3 nm (xcex5=4.86xc3x97104) 
The purity of the target compound proved to be 93.5% with liquid chromatography carried out under the same conditions as in Synthesis Example 1.
Now, compositions for processing silver halide photographic materials, which will be referred to as processing compositions hereinafter, of the present invention will be described in detail. The term xe2x80x9cprocessing compositionxe2x80x9d implies such that is used to process silver halide photographic materials in order to accomplish image formation, more concretely, means those for color development, bleaching, bleach-fix (blix), fixing, washing and stabilization. It can also include compositions for black-and-white development, reversal materials and for pre-bleaching. Those compositions may be in the form of solutions at working concentration as processing liquids for tank charging or for replenishing, or in the form of condensed solution. In the case where the processing compositions of the present invention are in the form of condensed liquid, they are diluted with a pre-determined amount of water prior to usage as tank liquid or replenisher. Though the compounds characterizing the present invention, when they are in solution form, have an excellent stability against precipitation formation, they can also be used in compositions in the form of granule, tablet, powder or slurry.
In the processing composition of the present invention, the concentration of the compounds represented by general formula (I) and/or (II) lies between 0.05 and 20 mmole/L at the working condition, preferably between 0.15 and 15 mmole/L, and more preferably between 0.2 and 10 mmole/L. In the form of condensed solution, which needs be diluted prior to usage, the concentration of the compounds cited above increases by the ratio of condensation.
The image forming method of the present invention uses the present processing composition in at least one processing step, or it can use the present processing compositions in two or more, or all the processing steps involved in the image forming method.
Among various methods of preparing the present processing composition, the following three methods give desirable results. However, in practicing the present invention, the preparation of the processing composition are not to be limited to those three methods at all.
[Method A] To a mixing tank charged with a small amount of water, component chemicals for the composition are added in turn under stirring.
[Method B] Firstly, component chemicals are blended, then the mixture is placed in a mixing tank, to which a small amount of water is added all at once.
[Method C] Necessary chemicals are first divided appropriately into sub-groups. Each group is separately dissolved in water or a water-miscible organic solvent to form a condensed solution, and then all the condensed solutions are mixed together.
Further, a method comprising each of the above methods partly is also practicable.
The processing composition of the present invention may be any of a color developer composition, a bleaching composition, a bleach-fix (blix) composition, a fixing composition, a rinse composition and a stabilizing composition.
The color developer compositions of the present invention include color developing agents. The well-known aromatic primary amine color developing agents are preferred;, in particular, p-phenylenediamine derivatives are most preferred. Some representative examples are listed below not with the purpose of limiting the scope of the invention to them. Some recent black-and-white photographic materials contain couplers that develop a neutral black dye image when processed with a general-purpose color developer. The processing composition of the present invention can be applied to such a type of photographic material, too.
N-1) N,N-diethyl-p-phenylenediamine
N-2) 4-amino-N,N-diethyl-3-methylaniline
-N-3) 4-amino-N-(xcex2-hydroxyethyl)-N-methylaniline
N-4) 4-amino-N-ethyl-N-(xcex2-hydroxyethyl)aniline
N-5) 4-amino-N-ethyl-N-(xcex2-hydroxyethyl)-3-methylaniline
N-6) 4-amino-N-ethyl-N-(3-hydroxypropyl)-3-methylaniline
N-7) 4-amino-N-ethyl-N-(4-hydroxybutyl)-3-methylaniline
N-8) 4-amino-N-ethyl-N-(xcex2-methane sulfonamidoethyl)-3-methylaniline
N-9) 4-amino-N,N-diethyl-3-(xcex2-hydroxyethyl)aniline
N-10) 4-amino-N-ethyl-N-(xcex2-methoxyethyl)-3-methylaniline
N-11) 4-amino-N-(xcex2-ethoxyethyl)-N-ethyl-3-methylaniline
N-12) 4-amino-N-ethyl-N-(3-carbamoylpropyl)-N-n-propyl-3-methylaniline
N-13) 4-amino-N-(4-carbamoylbutyl)-N-n-propyl-3-methylaniline
N-14) N-(4-amino-3-methylphenyl)-3-hydroxypyrrolidine
N-15) N-(4-amino-3-methylphenyl)-3-hydroxymethylpyrolidine
N-16) N-(4-amino-3-methylphenyl)-3-pyrolidine carboxamide
Among the p-phenylenediamine derivatives cited above, N-5), N-6), N-7), N-8) and N-12) and particularly N-5) and N-8) are preferred. These p-phenylenediamine derivatives are available in the form of sulfuric acid salt, hydrochloric acid salt, p-toluenesulfonicacid salt, naphthalene disulfonic acid salt, N,N-bis (sulfonylethyl)hydroxylamine salt, etc. They may be used in the composition in their free form.
The concentration of the aromatic primary amine developing agent described above in the working solution is generally from 4 to 100 mmole/L, preferably from 6 to 50 mmole/L, and more preferably from 8 to 25 mmole/L.
The color developer composition of the present invention can contain a compound which prevents the deposition of a color developing agent. Such typical compounds are poly(ethylene glycol)s, arylsulfonic acids, alkylsulfonic acids, or urea compounds described in JP-A-11-174643. Among these, particularly preferable ones that exert least adverse effects on photographic characteristics and are effective in deposition prevention are diethylene glycol, polyethylene glycol 300, p-toluenesulfonic acid and its salts, n-alkylsulfonic acids having 5 to 9 carbon atoms and their salts, or ethylene urea.
The color developer composition of the present invention can preferably contain compounds or preservatives that prevent the aerial oxidation of the color developing agent. Preferable inorganic preservatives include sulfite salts and hydroxylamine. They exhibit a marked preserving capability, which can be enhanced by a combined use of organic preservatives. Since sulfite salts and hydroxylamine exert undesirable effects on the photographic characteristics of certain types of materials during color development, the combined use of these two types are sometimes avoided or only organic preservatives are used.
Effective organic preservatives include hydroxyamine derivatives, hydroxysamic acids, hydrazides, phenols, xcex1-hydroxyketones, xcex1-aminoketones, saccharides, monoamines, diamines, polyamines, quarternary ammonium salts, nitroxy radicals, alcohols, oximes, diamides, condensed ring amines, cyclic amides, salycilic acid, polyethylenimines, alkanolamines and aromatic polyhydroxy compounds.
Of the organic preservatives, hydroxylamine derivatives described in JP-A-3-56456 and JP-A-3-33845 and compounds described in JP-A-3-33846 and JP-A-6-148841 are particularly preferred.
It is desirable to use hydroxylamine derivatives together with alkanolamines from the viewpoint of stability improvement of color developer in continuous processing. Particularly preferred compounds which are used in combination with hydroxylamines are triisopropanolamine and triethanolamine. Cyclic amide compounds can also be combined with hydroxylamine derivatives, among which xcex5-caprolactam is particularly suited.
The pH value of the color developer composition of the present invention is preferably 9.5 to 13.5, more preferably 12.0 to 13.5, and that of the color developer prepared therefrom is 9.0 to 12.2, and more preferably 9.9 to 11.2. Buffer agents are usually used to stabilize the pH of the developer. Preferable buffer agents include inorganic potassium or sodium salts such as carbonates, bicarbonates, phosphates, borates and tetraborates. Organic compounds such as 5-sulfosalycilic acid, xcex2-alanine, proline, tris-hydroxyaminomethane, etc. can also be preferably used. These compounds are mentioned not to limit the scope of the invention. The concentration of these buffer agents is not lower than 0.1 mole/L and more preferably between 0.1 and 0.4 mole/L as the color developer replenisher.
To the color developer composition of the present invention, various chelating agents can be added for preventing precipitation of calcium, magnesium, etc. One or more kinds of chelating agents can be used. Preferable compounds as the chelating agents include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine teteraacetic acid, N,N,N-trimethylene phosphonic acid, ethylenediamine-N,N,Nxe2x80x2,Nxe2x80x2-tetramethylene sulfonic acid, ethylenediaminesuccinic acid (s,s-isomer), 2-phosphobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,2-dihydroxybenzene-4,6-disulfonic acid, etc. The amount of chelating agent is determined so as to be sufficient to mask the metallic ion present in the color developer, being usually 0.1 g/L to 10 g/L.
Any of known development accelerators may be used in the color developer composition of the present invention when needed. Typical compounds include polyalkylene oxide, 1-phenyl-3-pyrazolidones, alcohols, carboxylic acids, etc.
Any of known anti-fogging agents may be used in the color developer composition of the present invention when needed. Typical anti-fogging agents include metal halides such as sodium chloride, potassium bromide, potassium iodide, etc., and organic compounds represented by nitrogen-containing heterocyclic compounds. Such organic anti-fogging agents include, for example, benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine, adenine, etc. Further, alkylcarboxylic acids, arylcarboxylic acids or saccharides may be added to the composition.
When the present invention is applied to the color development of color print photographic materials, the processing temperature is set preferably at 30 to 55xc2x0 C., more preferably at 35 to 50xc2x0 C., and still more preferably at 38 to 45xc2x0 C. The developing period is 5 to 90 seconds, preferably 8 to 60 seconds, and more preferably 10 to 45 seconds. The smaller replenishing amount is considered the better, and is appropriately 15 to 200 mL, preferably 20 to 120 mL and more preferably 30 to 60 mL, per 1 m2 of the photographic material to be processed.
In the case of color negative film, the processing temperature is 30 to 55xc2x0 C., more preferably 35 to 50xc2x0 C., and still more preferably 38 to 45xc2x0 C. The development period is usually 45 seconds to 5 minutes, preferably 60 seconds to 4 minutes, and more preferably 90 seconds to 3 minutes 15 seconds. The smaller replenishing amount is considered the better, and is appropriately 10 to 200 mL, preferably 12 to 60 mL and more preferably 15 to 30 mL, per one film roll for taking 24 pictures.
The color developer compositions in which the replenisher is condensed as disclosed in JP-A-11-174643, JP-A-11-194461 and JP-A-11-194462 are examples of preferred embodiments.
The bleaching and beach-fix compositions of the present invention can contain any known bleaching agents. Particularly, organic complex salts of Fe(III) exemplified by the complex salts of organic acids such as aminopolycarboxylic acids, citric acid, tartaric acid, malic acid, etc., persulfate salts, hydrogen peroxide, etc. are preferred. Two or more kinds of bleaching agent may be used together.
Among the compounds cited above, the organic complex salts of Fe(III) are particularly suited from the viewpoint of rapid working and protection of environment pollution. Favorable aminopolycarboxylic acids and their salts used to form complex salts with Fe(III) include ethylenediaminesuccinic acid (s, s isomer), N-(2-carboxylato ethyl)-L-aspartic acid, xcex2-alaninediacetic acid, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, glycol ether diamine tetraacetic acid, etc. and their sodium, potassium, lithium or ammonium salts. Among these compounds, the following are preferred due to the good photographic characteristics of their Fe (III) salts; ethylenediaminesuccinic acid (s, s isomer), N-(2-carboxylate ethyl)-L-aspartic acid, xcex2-alanine diacetic acid, methyliminodiacetic acid, ethylenediamine tetraacetic acid, diethylenetriaminepentaacetic acid, and 1,3-propylenediaminetetraacetic acid. They may be added as Fe (III) complex salts, or Fe complex salts may be formed in the bleaching solution by using a ferric salt such as sulfate, chloride, nitrate, ammonium nitrate, phosphate, etc. with a chelating agent such as aminopolycarboxylic acid. The chelating agent may be used in excess of the amount required to form its ferric complex salt. The working concentration of the bleaching agent in the bleaching or blix solution is from 0.01 to 1.0 mole/L, preferably from 0.05 to 0.5 mole/L and more preferably from 0.1 to 0.5 mole/L.
Buffer agents are preferably used in bleaching or blix solutions. Suitable buffer agents are chosen depending on the target pH value; suitable compounds include organic acid such as succinic acid, maleic acid, glycolic acid, malonic acid, fumaric acid, sulfosuccinic acid, acetic acid, etc., organic base such as imidazole, dimethylimidazole, etc. or those represented by general formulae (A-a) and (B-b) of JP-A-9-211819. The preferred range of the working concentration of buffer agent is 0.005 to 30 mole/L, and more preferably 0.05 to 1.5 mole/L. The pH range of bleaching solution is preferably from 2 to 7, a more preferable one being from 4 to 7. The pH range of blix bath is preferably from 3 to 8, and more preferably from 4 to 7.
The processing temperature for bleaching and fixing of photographic color print materials is preferably 35 to 55xc2x0 C., more preferably 35 to 50xc2x0 C., and still more preferably 38 to 45xc2x0 C. The processing time is usually 5 to 90 seconds, preferably 8 to 60 seconds, and more preferably 10 to 45 seconds. Generally speaking, the smaller replenishing amounts are the more desirable, but 20 to 200 mL per 1 m2 photographic material are appropriate. A more preferable range for this amount is 25 to 120 mL, still more preferable one being 30 to 50 mL.
In the bleaching of color negative films, the processing temperature is preferably 30 to 55xc2x0 C., more preferably 35 to 50xc2x0 C., and still more preferably 38 to 45xc2x0 C. The period of bleaching is preferably 12 seconds to 2 minutes, more preferably 15 seconds to 1 minute 15 seconds, and still more preferably 18 to 60 seconds. In general, the smaller replenishing amounts are the more desirable, but 2.5 to 50 mL per single 35-mm film roll for taking 24 pictures is considered appropriate. A more preferable range for this amount is 3 to 25 mL, still more preferable one being 4 to 12 mL.
The fixing agent used in the blix and fixing compositions of the present invention include known ones, i.e., thiosaulfate salts such as sodium thiosulfate and ammonium thiosulfate, etc., thiocyanate salts such as sodium thiosulfate and ammonium thiocyanate, ethylene bisglycolic acid, 3,6-dithia-1,8-octandiol, thioether compounds or thioureas both described in JP-A-4-317055, and water-soluble solvents for silver halide such as meso-ionic compounds described in JP-A-4-143757 and JP-A-4-230749. These compounds may be used solely or in combination. Preferable fixing agents are thiosulfate salts, among which ammonium thiosulfate is particularly preferred. The fixing agent concentration in the fixing or blix bath is preferably 0.3 to 2 mole/L, more preferably being 0.5 to 1.5 mole/L.
Buffer agents should be added to blix or fixing solutions. Suitable buffer agents include heterocyclic organic bases such as imidazole, dimethylimidazole, etc., aminoalkylene sulfonic acid such as taurine, or dibasic acids such as succinic acid, maleic acid and malonic acid. The pH value preferably lies between 3 and 8, and more preferably between 4 and 7.
The present blix and fixing compositions can preferably contain compounds that, as preservative, release sulfite ion such as sulfite salts, bisulfite salts, meta-bisulfite salts, etc. They may be in the form of potassium salt, sodium salt or ammonium salt. Further, arylsulfinic acid can also be used in the compositions such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid, p-aminobenzenesulfinic acid, etc. The concentration of these compounds in the working solutions is preferably 0.02 to 1.0 mole/L. Other useful preservatives include ascorbic acid, carbonyl bisulfite adduct and carbonyl compounds.
The blix and fixing compositions of the present invention can preferably contain compounds which improve image stability by forming stable silver ion, exemplified by mercapto nitrogen-containing heterocyclic compounds such as mercaptotriazole, aminomercaptotriazole, N-methylmercaptoimidazole, etc., or those which promote the wash-out of developing agent, exemplified by bis-amidines, bis-guanidines or monoamidines all disclosed in JP-A-5-303185. Furthermore, the blix and fixing compositions of the present invention can contain polymers such as polyethylene glycol, polyvinylpyrrolidone, etc., chelating agent, defoaming agent, fungicide, etc., depending on specific needs of the compositions.
The processing composition of the present invention can advantageously take the form of single package whereby all the components for the working solution are packed together for storage. However, in cases where a prolonged contact of certain components in color developer or blix compositions are not desirable, the compositions can take the form of two or three packages by dividing the components into appropriate parts. According to International Standard ISO5989, such forms are referred to as 1, 2 and 3 part constitutions. The present processing compositions do not lose their advantageous features and effects with any constitution. As for color developer compositions, particularly one-part constitution is most preferred.
The containers for the present processing composition may be made of various known materials depending on the properties of the contents. They may be made of a single material or of composite materials exemplified by one consisting of a highly air permeable material and an alkali-resistant one. From the viewpoint of reuse or recycling, the containers are preferably made of a single material. Suitable materials include polyester resins, polyolefin resins, acrylic resins, ABS resins, epoxy resins, polyamide resins such as nylon, polyurethane resins, polystyrene resins, polycarbonate resins, PVA, poly(vinyl chloride), poly(vinylidene chloride) and polyethylene resins. Among them, polyester resins such as poly (ethylene terephthalate), poly (ethylene naphthalate), etc, polyolefin resins such as polyethylene, polypropylene, etc. are preferably used for the present container as single material The most preferable material is polyethylene, and, in particular, high density one (HDPE).
The container materials used in the present invention may contain various pigments such as carbon black, titanium dioxide, calcium carbonate, etc, plasticizers compatible with the main plastic material, etc. Practically preferable container materials are those in which polyethylene occupies not less than 85% of the entire formulation and in which no plasticizer is added, and more preferable ones are those in which polyethylene occupies not less than 95% and in which no plasticizer is added.
The shape and structure of the container for the present processing composition can be arbitrarily designed to meet individual purposes. In addition to standard bottles, elastic type vessels disclosed in JP-A-1-235950, vessels having flexible dividing walls disclosed in JP-A-62-134626 can also be used. Those disclosed in JP-A-11-282148 are particularly suited for the present processing compositions as regards volume, space efficiency, self-standing nature, shape conservation and reuse/recyclability. Processing kits comprising a single cartridge in which multiple processing compositions all based on the present invention are charged in multiple containers all made of common materials and having a common shape and size are preferable embodiments of the invention. Such cartridges are disclosed in JP-A-2000-3014. The combination of the processing compositions is arbitrary for such cartridges. In the cartridges disclosed in JP-A-11-295858 and JP-A-11-288068, a developing composition, a blix one, and a fix one are combined, forming a practically desirable embodiment.
In the blix of color print materials to be applied to the present invention, the processing temperature, the blix period and the replenishing rate have already been described. In the fixing of color negative materials, the processing temperature is preferably 30 to 55xc2x0 C., more preferably 35 to 50xc2x0 C., and still more preferably 38 to 45xc2x0 C. The period of bleaching is preferably 20 seconds to 2 minutes, more preferably 30 seconds to 1 minute 40 seconds, and still more preferably 35 seconds to 1 minute 20 seconds. In general, the smaller replenishing amounts are the more desirable, but 4 to 60 mL per one 35-mm film roll for taking 24 pictures is considered appropriate. A more preferable range for this amount is 5 to 40 mL, still more preferable one being 6 to 30 mL.
To the rinse and stabilizing compositions of the present invention, compounds that prevent dye fading and stain formation caused by remaining magenta couplers can be added. Some examples of such compounds are formaldehyde, acetaldehyde, pyruvinaldehyde, formaldehyde-bisulfite adduct disclosed in U.S. Pat. No. 4,921,779, or N-methylol compounds disclosed in JP-A-5-34889. Further, arylsulfinic acid such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid, p-aminobenzenesulfinic acid, etc. Moreover, surfactants to promote water draining, chelating agents to soften hard water, buffer agents for pH adjustment, defoaming agent, fungicides, disinfectant, etc. may also be added depending on necessity.
The pH is preferably between 4 and 10, and more preferably between 5 and 8. Washing temperature, which can change depending on the applications and characteristics of the photographic materials, is usually set to 20 to 50xc2x0 C., and preferably 25 to 45xc2x0 C.
Photographic elements processed according to the present invention can contain ordinary silver halide as photo-sensitive material, including silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide, and mixtures of those. As an embodiment, a photographic element contains a high chloride content silver halide that consists of at least not less than 50 mole % and more preferably not less than 90 mole % of silver chloride. Such an element is often used as photographic color print material.
In another embodiment, at least one emulsion in the photographic element mainly consists of silver bromide (not less than 50 mole % being bromide). Most preferably, in such an embodiment, the photographic element contains at least one silver bromide emulsion that is used to record at least one color image as in color negative or color reversal films. Photographic elements that are processed according to the present invention can record monochromatic information or plural color information, and can have a magnetic recording layer that is already well known in the art.
Individual photographic elements are described in, for example, many Research Disclosures (RDs) including RD17643, pp.23-27, RD18716, pp.647-650. RD307105, pp.866-868 and pp.873-879 and RD36544,pp.501-541. These RDs describe useful silver halide emulsions (negative and positive types) and their preparing methods, various sensitizers, dye-forming couplers, dye image stabilizers, dyes, UV absorbers, filters, binders, hardening agents, plasticizers, lubricants, coating aids, surfactants, anti-static agents, matting agents, paper and film substrates, or image forming methods using negative and positive color image forming elements.